Síntese de pigmentos cerâmicos inorgânicos nanométricos e encapsulados com estrutura core-shell pela rota dos precursores poliméricos

The present work has as objective the development of ceramic pigments based in iron oxides and cobalt through the polymeric precursor method, as well as study their characteristics and properties using methods of physical, chemical, morphological and optical characterizations.In this work was used iron nitrate, and cobalt citrate as precursor and nanometer silica as a matrix. The synthesis was based on dissolving the citric acid as complexing agent, addition of metal oxides, such as chromophores ions and polymerization with ethylene glycol. The powder obtained has undergone pre-ignition, breakdown and thermal treatments at different calcination temperatures (700 °C, 800 °C, 900 °C, 1000 °C and 1100 °C). Thermogravimetric analyzes were performed (BT) and Differential Thermal Analysis (DTA), in order to evaluate the term decomposition of samples, beyond characterization by techniques such as BET, which classified as microporous materials samples calcined at 700 ° C, 800 º C and 900 º C and non-porous when annealed at 1000 ° C and 1100 º C, X-ray diffraction (XRD), which identified the formation of two crystalline phases, the Cobalt Ferrite (CoFe2O4) and Cristobalite (SiO2), Scanning Electron Microscopy (SEM) revealed the formation of agglomerates of particles slightly rounded;and Analysis of Colorimetry, temperature of 700 °C, 800 °C and 900 °C showed a brown color and 1000 °C and 1100 °C violet

Caracterização microestrutural e elétrica de La(FexNi1-x)O3 sintetizado pelo método da gelatina

The present work deals with the synthesis of materials with perovskite structure with the intention of using them as cathodes in fuel cells SOFC type. The perovskite type materials were obtained by chemical synthesis method, using gelatin as the substituent of citric acid and ethylene glycol, and polymerizing acting as chelating agent. The materials were characterized by X-ray diffraction, thermal analysis, spectroscopy Fourier transform infrared, scanning electron microscopy with EDS, surface area determination by the BET method and Term Reduction Program, TPR. The compounds were also characterized by electrical conductivity for the purpose of observing the possible application of this material as a cathode for fuel cells, solid oxide SOFC. The method using gelatin and polymerizing chelating agent for the preparation of materials with the perovskite structure allows the synthesis of crystalline materials and homogeneous. The results demonstrate that the route adopted to obtain materials were effective. The distorted perovskite structure have obtained the type orthorhombic and rhombohedral; important for fuel cell cathodes. The presentation material properties required of a candidate cathode materials for fuel cells. XRD analysis contacted by the distortion of the structures of the synthesized materials. The analyzes show that the electrical conductivity obtained materials have the potential to act as a cell to the cathode of solid oxide fuel, allowing to infer an order of values for the electrical conductivities of perovskites where LaFeO3 < LaNiO3 < LaNi0,5Fe0,5O3. It can be concluded that the activity of these perovskites is due to the presence of structural defects generated that depend on the method of synthesis and the subsequent heat treatment

Desenvolvimento de metodologias analíticas alternativas por cromatografia gasosa para análise de biodiesel

Since the beginning of the National Program for Production and Use of Biodiesel in Brazil, in 2004, different raw materials were evaluated for biodiesel production, trying to combine the agricultural diversity of the country to the desire to reduce production coasts. To determine the chemical composition of biodiesel produced from common vegetables oils, international methods have been used widely in Brazil. However, for analyzing biodiesel samples produced from some alternative raw materials analytical problems have been detected. That was the case of biodiesel from castor oil. Due the need to overcome these problems, new methodologies were developed using different chromatographic columns, standards and quantitative methods. The priority was simplifying the equipment configuration, realizing faster analyses, reducing the costs and facilitating the routine of biodiesel research and production laboratories. For quantifying free glycerin, the ethylene glycol was used in instead of 1,2,4-butanetriol, without loss of quality results. The ethylene glycol is a cheaper and easier standard. For methanol analyses the headspace was not used and the cost of the equipment used was lower. A detailed determination of the esters helped the deeper knowledge of the biodiesel composition. The report of the experiments and conclusions of the research that resulted in the development of alternative methods for quality control of the composition of the biodiesel produced in Brazil, a country with considerable variability of species in agriculture, are the goals of this thesis and are reported in the following pages

Síntese de pigmentos cerâmicos inorgânicos nanométricos pela rota dos precursores poliméricos

Considering the constant evolution of technology in growth and the need for production techniques in the ceramics area to move forward together, we sought in this study, the research and development of polymeric precursor method to obtain inorganic ceramic pigments. Method that provides quality to obtain the precursor powders of oxides and pigments at the same time, offers time and cost advantages, such as reproducibility, purity and low temperature heat treatment, control of stoichiometry. This work used chromium nitrate and iron nitrate as precursors. The synthesis is based on the dissolution of citric acid as a complexing agent, addition of metal oxides, such as ion chromophores; polymerization with ethylene glycol and doping with titanium oxide. Passing through precalcination, breakdown, thermal treatments at different temperatures of calcination (700 to 1100 oC), resulting in pigments: green for chromium oxide deposited on TiO2 (CrTiO3) and orange for iron oxide deposited on TiO2 ( FeTiO3). Noticing an increase of opacity with increasing temperature. Were performed thermal analysis (TG and ATD) in order to evaluate its thermodecomposition. The powders were also characterized by techniques such as XRD, revealing the formation of crystalline phases such as iron titanate (FeTiO3) and chrome titanate (CrTiO3), SEM, demonstrating formation of rounded particles for both oxides and Spectroscopy in the UV-Visible Region, verifying the potential variation and chromaticity os pigments. Thus, the synthesized oxides were within the requirements to be applied as pigments and shown to be possible to propose its use in ceramic materials

Obtenção e Caracterização Físico-Química do Sistema Compósito PEG-TiO2

Hybrid systems formed from polymers and transition metals have now their physical and chemical properties extensively investigated for use in electronic devices. In this work, Titanium Dioxide (TiO2) from the precursor of titanium tetrabutoxide and the composite system Poly(Ethylene Glycol)-Titanium Dioxide (TiO2-PEG) were synthesized by sol-gel method. The PEG as acquired and TiO2 and composites powders were analyzed by X-Ray Diffraction (XRD), Spectroscopy in the Infrared region with Fourier transform (IRFT), Thermogravimetric Analysis (TGA), Scanning Electron Microscopy (SEM) and Electrochemical Impedance Spectroscopy (EIS). In the XRD analysis were observed in the TiO2 crystal faces of one of its polymorphs - anatase phase, crystal planes in Poly (Ethylene Glycol) with considerable intensity and in the composite systems the mixture of crystal faces of their precursors isolated and reduction of crystallinity. The TG / DTG suggested increasing the thermal instability of PEG in the composite powders as TiO2 is incorporated into the system. Spectral analysis presented in the infrared overlapping bands for the polymer and metal oxide, reducing the intensity of symmetric stretching of ligand groups in the main chain polymer and angular deformations; were observed using SEM micrographs of the morphological changes suffered by composite systems with the variation of the oxide concentration. Analyses by impedance spectroscopy indicated that the increased conductivity in composite occurs in line with the addition of the metal oxide concentration in the composite system

Obtenção de polímeros graftizados de quitosana e estudo das propriedades físico-químicas para aplicação na indústria do petróleo

Chitosan is a biopolymer derived from the shells of crustaceans, biodegradable, inexpensive and renewable with important physical and chemical properties. Moreover, the different modifications possible in its chemical structure generate new properties, making it an attractive polysaccharide owing to its range of potential applications. Polymers have been used in oil production operations. However, growing concern over environmental constraints has prompted oil industry to search for environmentally sustainable materials. As such, this study sought to obtain chitosan derivatives grafted with hydrophilic (poly(ethylene glycol), mPEG) and/or hydrophobic groups (n-dodecyl) via a simple (one-pot) method and evaluate their physicochemical properties as a function of varying pH using rheology, small-angle Xray scattering (SAXS), dynamic light scattering (DLS) and zeta potential. The chitosan derivatives were prepared using reductive alkylation under mild reaction conditions and the chemical structure of the polymers was characterized by nuclear magnetic resonance (1H NMR) and CHN elemental analysis. Considering a constant mPEG/Chitosan molar ratio on modification of chitosan, the solubility of the polymer across a wide pH range (acidic, neutral and basic) could only be improved when some of the amino groups were submitted to reacetylation using the one-pot method. Under these conditions, solubility is maintained even with the simultaneous insertion of n-dodecyl. On the other hand, the solubility of derivatives obtained only through mPEG incorporation using the traditional methodology, or with the ndodecyl group, was similar to that of its precursor. The hydrophilic group promoted decreased viscosity of the polymer solutions at 10 g/L in acid medium. However, at basic pH, both viscosity and thermal stability increased, as well as exhibited a pronounced pseudoplastic behavior, suggesting strong intermolecular associations in the alkaline medium. The SAXS results showed a polyelectrolyte behavior with the decrease in pH for the polymer systems. DLS analyses revealed that although the dilute polymer solutions at 1 g/L and pH 3 exhibited a high density of protonated amino groups along the polymer chain, the high degree of charge contributed significantly to aggregation, promoting increased particle size with the decrease in pH. Furthermore, the hydrophobic group also contributed to increasing the size of aggregates in solution at pH 3, whereas the hydrophilic group helped reduce their size across the entire pH range. Nevertheless, the nature of aggregation was dependent on the pH of the medium. Zeta potential results indicated that its values do not depend solely on the surface charge of the particle, but are also dependent on the net charge of the medium. In this study, water soluble associative polymers exhibit properties that can be of great interest in the petroleum industry

Conservação de material genético de espécies silvestres do bioma caatinga utilizando a manipulação oócitos inclusos em folículos ovarianos pré antrais (MOIFOPA)

The objective of the present thesis was to use the manipulation of oocytes enclosed in preantral follicles (MOEPF) as a tool for the female gametes rescue and optimization, from wild species of Caatinga biome. The thesis was divided into 4 experiments. At first experiment, it was performed the estimative and description of the agouti (Dasyprocta leporina) preantral follicles (PF) histologic and ultrastructural features, in which it was estimated 4419.8 ± 532.26 and 5397.52 ± 574.91 follicles for the right and left ovary, respectively, and the majority (86,63%) belonged to the primordial follicles category (P<0.05). Most of the population consists of morphologically normal follicles (70.78%), presenting a large and central nuclei and uniform cytoplasm. At ultrastructural evaluation it was verified the presence of a great number of round mitochondrias associated to lipid droplets. In the second experiment, it was performed the estimative and description of yellow-toothed cavies (Galea spixii) PF characteristics, also, the evaluation of the effect of solid surface vitrification (SSV) on the in situ PF morphology. The total of 416.0 ± 342.8 PF was estimated for the ovary pair and the presence of a large quantity of primary follicles (P<0.05) was evidenced. Most of the PF was morphologically normal (94.6%), in which the oocyte nuclei presented condensed granules of heterochromatin. Round or elongated shaped mitochondria constituted the most abundant organelles. In regard of the SSV, the protocol using the dimethylsulfoxide (DMSO) 3M possibility the preservation of 69.5% of morphologically normal PF, which was evidenced by the light and transmission electronic microscopy. At third experiment, the evaluation of the SSV procedure on the morphology and viability in situ PF form collared peccaries (Pecari tajacu) was performed. No differences were observed among treatments, in which the use of DMSO, ethylene glycol (EG) and dimethylformamide (DMF) as cryoprotectants, regardless its concentration, promoted the morphology preservation of much than 70% of PF. Concerning the PF viability, the DMSO and EG promoted the best preservation. The fourth experiment aimed to evaluate the effect of α MEM+ or TCM199 associated or not to 50 ng of FSHr on the morphology, activation and growth of collared peccaries PF, in vitro cultured (IVC) during 1 or 7 days and the effect on the extracellular matrix (ECM). After 7 days of IVC only the use of TCM199/FSH maintained the proportion of intact PF, similar to day 1(63.2%), however, no differences were observed among treatments (P>0.05). Also, an improvement of the proportion of intact growing PF was verified (P>0.05). By the Ag-NOR analysis it was observed that only the treatment using TCM199/FSH promoted the maintenance of cell proliferation similar to day 1 (P>0.05). The picrosirius red stain revealed that ECM remained intact in all treatments (P>0.05). Thus, as the general conclusion, the use of MOEPF in the refereed species allowed the knowledge of aspects related to its reproductive morphology and physiology, enabling the germplasm conservation, with the possibility of germplasm bank formation, as the elucidation of mechanisms related to the PF survive and in vitro development.

Síntese de pigmentos cerâmicos inorgânicos nanométricos e encapsulados com estrutura core-shell pela rota dos precursores poliméricos

The present work has as objective the development of ceramic pigments based in iron oxides and cobalt through the polymeric precursor method, as well as study their characteristics and properties using methods of physical, chemical, morphological and optical characterizations.In this work was used iron nitrate, and cobalt citrate as precursor and nanometer silica as a matrix. The synthesis was based on dissolving the citric acid as complexing agent, addition of metal oxides, such as chromophores ions and polymerization with ethylene glycol. The powder obtained has undergone pre-ignition, breakdown and thermal treatments at different calcination temperatures (700 °C, 800 °C, 900 °C, 1000 °C and 1100 °C). Thermogravimetric analyzes were performed (BT) and Differential Thermal Analysis (DTA), in order to evaluate the term decomposition of samples, beyond characterization by techniques such as BET, which classified as microporous materials samples calcined at 700 ° C, 800 º C and 900 º C and non-porous when annealed at 1000 ° C and 1100 º C, X-ray diffraction (XRD), which identified the formation of two crystalline phases, the Cobalt Ferrite (CoFe2O4) and Cristobalite (SiO2), Scanning Electron Microscopy (SEM) revealed the formation of agglomerates of particles slightly rounded;and Analysis of Colorimetry, temperature of 700 °C, 800 °C and 900 °C showed a brown color and 1000 °C and 1100 °C violet

Caracterização microestrutural e elétrica de La(FexNi1-x)O3 sintetizado pelo método da gelatina

The present work deals with the synthesis of materials with perovskite structure with the intention of using them as cathodes in fuel cells SOFC type. The perovskite type materials were obtained by chemical synthesis method, using gelatin as the substituent of citric acid and ethylene glycol, and polymerizing acting as chelating agent. The materials were characterized by X-ray diffraction, thermal analysis, spectroscopy Fourier transform infrared, scanning electron microscopy with EDS, surface area determination by the BET method and Term Reduction Program, TPR. The compounds were also characterized by electrical conductivity for the purpose of observing the possible application of this material as a cathode for fuel cells, solid oxide SOFC. The method using gelatin and polymerizing chelating agent for the preparation of materials with the perovskite structure allows the synthesis of crystalline materials and homogeneous. The results demonstrate that the route adopted to obtain materials were effective. The distorted perovskite structure have obtained the type orthorhombic and rhombohedral; important for fuel cell cathodes. The presentation material properties required of a candidate cathode materials for fuel cells. XRD analysis contacted by the distortion of the structures of the synthesized materials. The analyzes show that the electrical conductivity obtained materials have the potential to act as a cell to the cathode of solid oxide fuel, allowing to infer an order of values for the electrical conductivities of perovskites where LaFeO3 < LaNiO3 < LaNi0,5Fe0,5O3. It can be concluded that the activity of these perovskites is due to the presence of structural defects generated that depend on the method of synthesis and the subsequent heat treatment

Desenvolvimento de metodologias analíticas alternativas por cromatografia gasosa para análise de biodiesel

Since the beginning of the National Program for Production and Use of Biodiesel in Brazil, in 2004, different raw materials were evaluated for biodiesel production, trying to combine the agricultural diversity of the country to the desire to reduce production coasts. To determine the chemical composition of biodiesel produced from common vegetables oils, international methods have been used widely in Brazil. However, for analyzing biodiesel samples produced from some alternative raw materials analytical problems have been detected. That was the case of biodiesel from castor oil. Due the need to overcome these problems, new methodologies were developed using different chromatographic columns, standards and quantitative methods. The priority was simplifying the equipment configuration, realizing faster analyses, reducing the costs and facilitating the routine of biodiesel research and production laboratories. For quantifying free glycerin, the ethylene glycol was used in instead of 1,2,4-butanetriol, without loss of quality results. The ethylene glycol is a cheaper and easier standard. For methanol analyses the headspace was not used and the cost of the equipment used was lower. A detailed determination of the esters helped the deeper knowledge of the biodiesel composition. The report of the experiments and conclusions of the research that resulted in the development of alternative methods for quality control of the composition of the biodiesel produced in Brazil, a country with considerable variability of species in agriculture, are the goals of this thesis and are reported in the following pages